Poly-azo dyestuffs



Patented June 21, 1932 V UNITED STATES 1,863,792 PATENT, OFFICE WINFRID HENTRICH, OF WIESDORF-ON-THE-RHLHE, ANDJOSEPH HILGER,OF COLOGNE- MULHEIM, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., 01? NEW YORK, N. Y., A CORPORATION OF DELAWARE POLY-A20 DYESTUFFS No Drawing Application filed June 27, 1928, Serial No. 288,803, and in Germany'J'uly 13,1927.

Our invention relates to new polyazo dyestuffs and a process of preparing the same. More particularly it relates to the azo dyestuffs of the general formula:

wherein R- stands for the residue of an azo compound containing in its complex a henzene or naphthalene nucleus in which two para-positions are substituted by azo groups, and which is furthermore substituted by an HOaS ether group; one X represents the CO- group; the other two Xs represent CO "or CONH; n represents the numeral 1 or 2, P stands for a coupling component of the group consisting of the pyrazolones, aceto acetic acid arylamides, the methylketol compounds, sulfazones, 1.3-dihydroxyquinoline and such salicylic acid compounds as are capable of being coupled, and wherein the aromatic nuclei may be further substituted zene or naphthalene series which is capable amino-naphthol or an N-amino-benzoylamino -benzoyl peri amino naphthol, in a which compound one or more of the CO.NH linkages can be replaced by the NH.CO.NH. group and which may contain substituents in the naphthalene or in the benzene nucleus, then diazotizing" again and finally coupling suitably with a pyrazolone, a derivative of a B-ketonic aldehyde, methyl ketol or an analogue or substitution product thereof, a sulfazone, 1.3-dihyd'roxy-quinoline,

salicylic acid or a derivative thereof; The

final diazotization. and coupling may be effected on the fibre, in which-case a coupling component is employed, containing a reactive methylene group, but no sulfonic acid 1 group.

Valuable green .trisand tetrakisazo dyestuffs, distinguished by a. high affinity for the vegetable fibre and very good fastnessto light, are thus obtained.

The N amino benzoyl amino benzoylamino-benzoyl-peri -amino-naphtholand N- amino benzoyl amino benzoyl peri amino naphthol can, for example, be compounds of the following, formulae:

on NBC OONHG OONHO CONE;

on NBC o-O-Nno o-Qon,

I NH:

HOaS- sosn on NBC ONHONHC oQo-ona v I i V NHz 1103s SO3H Among the amino-ethers of the benzene series applicable as intermediate. components may be mentioned, for example, 3-amin'o-4- methoxy-l-methyl-benzene or the corresponding ethoxy or hydroxy-ethoxy compound or the sulfuric acid ester thereof of the following formula:

CHz-OHFOSOaH or also the (4-1nethyl-2-amino phenoxy)-,B- propionic acid: p

om-om-ooon and similar compounds.

hydroxy-ethyl being capable of Among the compoundsof thenaphthalene series may be mentioned the following: 1-

amino'- 2 hydroxy -naphthalene ethyl-ether, the (l-amino-Q-naphthoxy) -,8'-p ropionic acid i i 7 NH: V l

V I I V wocm-onhcoon;

the sulfonic acid ester of l-amino-2-naphthol ether the 6- (or 7-) monosulforiicacids of all these 1-amino-2-naphthol etliers, or also the amino-7-naphthol-methyl-ether J NH:

such as I In this manner dyeings or printings are likewise obtained, the shades'of which are very fast to washing, soaping and light. The printings possess the important property of pure and permanent white discharge. v i

In the new series of generally greentrisand tetrakisazo compounds produced according well on cotton.

f The combination 1 amino 8 dine. The formation of the dyestu fi' takes place immediately accompanied by a deep blue coloration of the solution. The resulting 'dyestufi is salted out, filtered and then dissolved in water. 70 parts by weight of sodium nitrite areadded, after which the solution is acidified with hydrochloric acid at room temperature.

complete, after. stirring for one hour the Diazotization is soon diazodisazo compound is salted out, filtered and made into a paste with a little water, the paste being added with stirring to a solution of 217 parts by weight of the pyrazolone obtained from meta-hydrazine-benzoic"acid and acetoacetic ester, in 5000 parts by weight of water and 300 parts by weight of sodium carbonate. Coupling proceeds quickly, yielding a clear green dyestufl, which, is worked up in the customary manner. The

dyestuff dyes the vegetable fibre very well, a

cleargreen-of excellent fastness to light resulting. v

.-A very remarkable green direct dyeing dyestuflisobta'ined byreplacing in'the above example the 1.8-amino naphthol-3.6-disu1- fonic acid by the 1.8-amino-naphthol-5.7-

.disulfonic acid, the 3-amino-4-cresol-ethyletherby the (4'-methyl-2'-amino-phenyl)-,8

propionic acid and the4"-amino-benzoyl-4- amino benzoyl 1 amino S-hydroxy-napthalene 3.6-disulfonic acid by thev compound:

" i on NHQONH-ONHGOO-O-OH:

'NHI" "finally the 3-carboxy-phenyl-methyl- "pyrazolone by the pyrazolone obtained from 4-chloro-2-hydrazine-benzoic acid and acetoacetic ester. A very clear green dyestufi' is likewise obtained very fast to light and dyei hydroxynaphthalene-3.G-disulfohic acid 3-am-ino-4- cresol-hydroxyethyl-ether of the formula:

ing to the above process are dyestuffsof extraordinary purity and yellowtinge. Until now it has been impossible to obtain such shades with any uniform substantive green dyestulf,

either by direct dyeing or developing.

The following examples illustrate our invention,"without limiting it thereto Ewample 1-482 parts by weight of the azo dyestuff obtained from. diazotized 1- amino-8-naphthol-3.6-disulfonic acid and 3- amino-et-cresol-ethyl ether are diazotized in the customary manner. The diazo com-' 7 v v pound is coupled at 5 C. with a solution pre- 7, I

pared from 575 parts by weight of 4-aminobenzoyl 4' amino benzoyl-1-amino-8-napthol 3.6-disulfonic acid, 5000 parts by weight of water, parts by weight of concentrated ammonia'and 1100 parts by weight of pyri- 1-amino napthalene-7-sulfonic amino benzoyl 4 amino-.benzoyl-4-amino -benzoyl-1-amino 8-hydroxy-naphthalene-3.6-

' di-sulf onic .acid the pyrazolone obtained from. ,3-hydrazine-3 met-hoxy- 2 hydroxybenzoic acid and acetoacetic ester of the formula c, a

' coon ou --o-.'. 'N- i OH:Q0/

produced the samema'nner'dyes cotton, for 'example, from a sodium sulfate bath, in clear grelpn shades which are even more fast to lig t. y

Valuable clear green dyeings fast. to light and washing are'obtained by dyeing the fibre from a sodium sulfate bath with the disazo dyestufi' (for example, that from 1.8-aminonaphthol-4.7-disu1fonic acid, 3-amino-4-cresol-ethyl-ether and i-amino-benzoyl-4- amino -benz.oyl l-amino -8 naphthol 3.6- disulfonic acid) diazotizing on the fibre and developing with methyl-phenyl-pyrazolone.

Example 2.-The diazoazo compound produced in the customary manner from 520v parts by weight of the azo dyestufi" from diazotized 4.5-dichloro-analine 2 sulfonic acid and 1-amino-Q-naphthol-ethyl-ether-6- sulfonic acid, is combined at 5 to 10C. with a 7 solution prepared from 575 parts by weight light. Printings of the dyestuff, produced in an analogous manner are very fast to" soaping and capable of pure white discharge.

Similar and in some cases even clearer dyestufi's are produced by replacing 4.5-dichloro-aniline-Q-sulfonic acid by aniline-'2- sulphonicacid, or 3-chloro-2-amin0-toluene- 5-sulfonic acid or 1.8-dimethyl-4-amino-benzene-5-sulfonic acid, or 2-amino-naphthalene-8-sulfonic acid, or l-amino-naphthalene 2-sulfonic acid or also by the amino monoazo dyestufi' from 2-amino-naphthalene-8-sul fonic acid and 3-toluidine or'bya similar compound. The l-amino 2 naphthol 'ethyl ether-(i-sulfonic acid can be replaced by the amino-naphthol-ethers above mentioned and instead of the 4"-amino-benzoyl-4'-aminobenzoyl-l-amino 8 hydroxy naphthalene- 3.6-disulfonic acid a thrice benzoylated compound of this kind such as acompound of the formula:

HQaS- SO33 can be used.

Example 3.The diazo-azo compound pre: pared as described in Example 3 from 520 parts by weight of the azo dyestufi' from .diazotized 4.5-dichloro-aniline 2 sul'fonic acid and l-amino-Q-naphthol-ethyl-ether-(isulfonic acid, is coupled in. accordance. with the directions of the previous examples with 587 parts by weight of 3"'-amino-4-methoXy-benzoyl-4--amino-benzoyl 1 amino 8- hydroxy-naphthalene-3.6-disulfonic. acid of the formula I NH], I

A disaZo dyestuff results, dyeing cotton a 7 clear greenish blue, which when diazotizedon the fibre and dev'elop'ed .with methylphenyl-pyrazolone yields a very pure green fast to washing and light.

By using as the first component the tetrazotized 4.4 diamino-diphenyl-urea-3.3-disulfonic acid of the formula:

NH-G ONH HzN- N Hz soan scan a greenish blue dyestufi is'likewiseobtained, which on developing with methyl-phenylpyrazolone. on the fibre yields a particularly clear green very fast to light, washing and;

topping. The shade is somewhat more yellow than that of the dyestufi in theabove example.

Green dyeings on cotton which are likewise pure and fast are obtained by coupling the 'diazotized l-amino-Q-sulfo-oxanilic acid 7 7 HOQC-CONHQNJQ with v 1 amino naphthalene methyl thioethenfurther diazotizmgand coupling with 4"-aminobenzoyl-3amino-tf-methoxy benzoyl-1-amino-8-hydroxy-naphthalene 3.6 disulfonic acid, dyeing the resulting "bluish green amino disazo dyestufl in the customary manner, diazotizing' on the fibre and developing with methyl-phenyl pyrazolone,;

Weclaim: ,g 1 1. In a process for producing polyazodyestuffs,the step whichcomprises coupling a further diazotized aminoazo-compound being .obtained from a compound of the group consisting of diazo and diazoazo compounds and from an ether of the: group consisting of oxy and thio ethers of the benzene and naphtha lene series, coupling in para-position to the amino group with a compound of the group consisting of N-aminobenzoyl-amino-benzoyl-amino-benzoyl-peri-amino naphthol and N amino benzoyl amino benzoyl peri I amino-naphthol in which compounds a part of the ,CONH linkages may be. substituted by --NHCO NH linkages and in which the naphthalene andbenzene nuclei rnay be further substituted by substituents' HOaS- pound capable of being coupled.

2. As a new product the azodyestufi of the following probable formula:' j

our]

soil

which is in a dry state adark powder of a bronze-dike luster, easily soluble in water on NHbo-ONHOOO-NQI r I a i r,

"pa-ble of being coupled andwherein the aro matic nuclei may be further substituted by substituents selected from the group consisting. ofhalogen, alkyl, alkoxy, substituted alkoxy, the thio ether group, the. sulfonic acid group and the carboxylic acid group, the said new products being. in the dry state dark powders of a bronze-like luster, being easily soluble in water with a clear green coloration, and dyeing cottonie xtremely green shades havingayellow tint.v

GQOH- 4:. As new products the azo dyestuffs of the general formula:

dyeing cotton clear green shadesvery fast to light.

3. As new products general formula:

the azo dyestuffs of the wherein Rstands for the residue of an azo compound containing in its complex a benzene or naphthaline nucleus inwhich two para-positions are substituted by azo groups, and "which is furthermore substituted by an ethergroup, one X- represents the CO-group, the other two Xs group consisting of the pyrazolones, aceto acetic acid arylamides, the methylketol compounds, Vsulfazones, '1.3-dihydroxyquinoline and such salicylic acid compounds as are ca,-

represent CO or CONH, n representsthe numeral 1 or '2, P stands fora coupling component of the wherein R stands for the residue of an azo compound containing 1n its complex a benzene or-naphthalenenucleus in'which two para-positionsaresubstituted by azo groups,

and which is furthermore substituted by an ether group, n represents the numeral 1 or 2 V and whereinthe aromatic nuclei maybe further substituted by substituents selected from the group consisting of: halogen, alkyl, alkoxy, substituted alkoxy, the'thioether group,-the sulfonic acid group and the carboxylic acid'group, the said new products being inthe' dry state dark powders ofa bronze-like luster, being easily soluble vin water with a clear green coloration and dyeing cotton extremely green shades, having a yellow tint.

' 5. As new products the azo dyestuffs of the general formula: 7

wherein R represents a benzene or naphthalene nucleus which maybe substituted by halogen, alkyl, the hydroXy group or the sulfonic acid group and n represents the numeral 1 or 2, the said new products being in the dry state dark powders of a bronze-like luster, being easily soluble in water with a clear 5 green coloration and dyeing cotton extremely green shades having a yellow tint.

6. As new products the azo dyestuffs of the general formula:

HOaS- 803B wherein R represents a benzene or naphthalene nucleus which may be substitued by halogen, alkyl, the hydroxy group or the sulfonic acid group, n represents the numeral 1 or 2, Y represents alkyl, alkyleneOI-I, alkylene.O.SO H, alkylene.COOH and wherein the benzene nucleus A may be substituted by the carboxylic acid group, halogen, alkyl or alkoxy, the said new products being in the dry state dark powders of a bronze-like luster, being easily soluble in water with a clear green coloration and dyeing cotton extremely green shades having a yellow tint.

In testimony whereof we have hereunto set our hands.

WINFRID HENTRICH. JOSEPH HILGER. 

